Insecticidal compositions and methods of killing insects using n-allyl phosphorothioamidates

ABSTRACT

The present invention is directed to insecticidal compositions containing a phosphorothioamidate of the formula   WHEREIN R1 is methyl or ethyl and R2 is an alkyl having 1 to 4 carbon atoms, and to its use in killing injurious insects in agriculture.

United States Patent [191 Hirano et a].

[ Nov. 5, 1974 INSECTICIDAL COMPOSITIONS AND METHODS OF KILLING INSECTS USING N-ALLYL PHOSPHOROTHIOAMIDATES [75] Inventors: Masachika Hirano, Minoo; Kunio Mukai, Nishinomiya; Hisami Takeda; Katsutoshi Tanaka, both of Takarazuka, all of Japan [73] Assignee: Sumitomo Chemical Company,

Limited, Osaka, Japan [22] Filed: Sept. 19, 1973 [21] Appl No.: 398,851

Related US. Application Data [62] Division of Ser. No. 197,923, Nov. ll, 1971, Pat. No.

[30] Foreign Application Priority Data Dec. [7, 1970 Japan 45-ll4365 [52] US. Cl. 424/216, 424/DIG. 8 [5 1] Int. Cl. A0ln 9/20, AOln 9/36 [58] Field of Search 424/216, DIG. 8

Primary Examiner-Albert T. Meyers Assistant Examiner-Allen J. Robinson Attorney, Agent, or Firm-Stevens, Davis, Miller & Mosher 5 7 ABSTRACT The present invention is directed to insecticidal compositions containing a phosphorothioamidate of the formula wherein R is methyl or ethyl and R is an alkyl having 1 to 4 carbon atoms, and to its use in killing injurious insects in agriculture.

2 Claims, No Drawings Compound No.

INSECTICIDAL COMPOSITIONS AND METHODS OF KILLING INSECTS USING N-ALLYL PHOSPIIOROTIIIOAMIDATES This is a division of application Ser. No. 197,923, filed Nov. 11, 1971 now U.S. Pat. No; 3,786,118. 5

This invention relates to a novel phosphorothioamidate having the formula [I],

CHZ=CI-IOHINBI 0 wherein R is as defined above, and M is an alkali metal, with a halide having the formula [III],

Hal-(CH -S-R [111] wherein R is as defined above, and Hal is a halogen, in a solvent.

Examples of the said solvent are polar solvents such as alcohols (methyl alcohol, ethyl alcohol), acetone and water. The reaction temperature and the reaction time depend on the solvent to be used, and usually the reaction may be completed for one to several hours under reflux.

Typical examples of the phosphorothioamidates thus prepared are as follows, but the scope of the present invention is, of course, not limited thereto.

Formula (1) CHFCHCHgNH 0 CzHsO SCH2CH S Cg'Ha (2) GHFCHOHNH O CHaO S--OH1CHgSC Hv(n) (5) CHFOHCHgNH O CgHrO S-CHzCHzS CH3 The phosphorothioamidates [I] are suitable for controlling injurious insects, particularly in agriculture. Examples of the'injurious insects controlled effectively by the phosphorothioamidates [I] are, for example, planthoppers, mites, borers, scales and mealybugs, and

nematodes, and other Lepidoptera, Diptera, Coleoptera, l-lemiptera, and other arthropoda can be also controlled by them.

There are usually known as systemic actions either action that chemicals penetrate into tissues of plants and animals, or action that they move therein after the penetration. It is notable that the phosphorothioamidates [I] have both excellent systemic actions. and moreover have biological activities such that by use of a concentration lower than a lethal one of the phosphorothioamidates [I], a transformation of insects is caused to be disturbed and a normal propagation is prevented. Further, the phosphorothioamidates [l] have so excellent contact insecticidal effects that they can effectively control insects and mites having power of resistance to the conventional biological chemicals.

As the compounds analogous to the present compounds [I], there are known in the specifications of U.S. Pat. No. 3,019,250, DAS No. 1,077,215 and DAS No. 1,135,905, a phosphate having the formula,

wherein R and R are as defined above, and A is hydrogen or an alkyl. In order to substantiate a superiority of the present compounds in'insecticidal effects to the known compounds mentioned above, a test example is given as follows.

Test Example Into a flower pot having about 10 cm in diameter 18 to 23 rice plants per pot were grown up to 3 to 4 leaves stage, and was sprayed thereon each 1,000 fold emulsion with water of the compounds in a form of 50 percent emulsifiable concentrate by means of a turntable, and was air-dried. Each pot was covered with a wire cage, and 20 to 30 adults of smaller brown planthoppers were released thereinto. The dead and alive were observed after 24 hours. Further the planthoppers were released according to the lapse of days to know the residual effects of the compounds. The results are as shown in-the following Table.

Days elapsed after the spraying and lethal rstlo (percent) 1 4 7 11 Compound day days days days Present compound:

2 CzHsO S-(CH:)rS-C2Ht CHsHN O 77.8 63.4 71.1 12.4

2 ClHsO S-(CHzh-S-CzHu CIHsHN O 93.4 66.7 51.4 10.0

a C1130 S-(CHflr-S-CH:

The compound disclosed in Example 12 01 U.S.P. No 3,019,250 "The compound disclosed in Example 28 of the old U .I.

q 'Thc compound disclosed in DAS N 0. 1,077,215.

The present compounds [I] may be used as it is without addition of other components, and may be combined with an carrier in order to form preparations Elementary Analysis Calculated Found as C H NO PS P 11.50 10.97 S 23.80 23.88 N 5.20 5.09

Example 2 According to the procedure similar to that of Example l, the following compounds are obtained.

Ex- Compound obtained ample Thiophoaphote Halide No. Refractlvo Phoapherothioemidate index Elementary analysis P S N 2 Potsnaium O-mathyl- Ethylthioethyl O-Methyl-S-(Z-ethyl- 30-5 Calc'd 12.13 25.11 5.49

N-ell 1 has horcchloride thioeihyU-N-allyl- N 1.5215

.3 P P D (ea C H NO PS thioenidete phosphorcthzoamdate 8 1.8 2 2 I Found 12.00 24.95 5.24

Potassium O-methyl- Z-Methylthioetlryl -Methy1-S-( Z-methyl- 26.0 Calc'd 12.84 26.57 5.80 3 N-allylpheaphorothiochloride thioethyU-lll-a11y1- 11 1.5301 (as 7 No PS midate phnaphorothmemdate 16 2 2 Found 12.74 26.71 5.52

Potassium 0-ethy1- 2-Metby1thioethy1 O-Ethyl-S-(Z-methylas o Colc'd 12.13 25.11 5.49 4 N-ellylphoaphorochloride thicethyU-lll-c11y1- N 1.5244 (as c a N0 PS thioamidnte phoephurothmamdete 8 10 2 2 Pound 11.77 25.42 5.37

For example, multi-purpose preparations may be prepared by the combination with the other organic phosphorus insecticides such as Sumithion (a trade mark of Sumitomo Chemical Co., in Japan) and Dimetoate, pyrethroid insecticides such as Allethrin and Pyrethrin, organic chlorine insecticides such as BHC and DDT, carbamate insecticides such as 3,4-dimethylphenyl-N- methylcarbamate, 2-sec.-butylphenyl-N'- methylcarbamate, 3-methylphenyl-N-methylcarbamate and 1-naphthyl-N-methylcarbamate, synergists, repellents, attractants and other analogues, and as the results thereof, a certain synergistic effect may be expected.

The present invention will be illustrated in more detail with reference to the following examples, which are only illustrative but not limitative. Percent and part are by weight.

" SYNTHESIS OF THE COMPOUND [1] Example 1 hydrous sodium sulfate, and the chloroform is removed by distillation under a reduced pressure, whereby 11.4

g of O-ethyl-S-(Z-ethylthioethyl)-N-allyl-phosphorothioamidate is obtained as a yellow oil, N 1.5183.

PREPARATION OF THE PESTICIDAL COMPOSITION Example 5: Emulsifiable Concentrate Active ingredient Solvent Emulsifrer Com- (1) 50 Xylol 3O *Sorpol -2020 20 pound do. (5) 20 Cyclohexanone 50 do. -2539 30 Note:

' Sorpol: a trade mark of Toho Chem. Cc.. in Japan.

Example 6: Wettable Powder Into 55 parts of 200 mesh tale, is added dropwise a mixture of 40 .parts of the compound 141 1 1 an emulsifier (Sorpol-2492: a trade mark of Toho Chem. Co., in Japan), while being stirred well in a mixer,- whereby a wettable powder is obtained. In a practical use, the powder is diluted with water.

Example 7: Granule Each compound, a binder and a diluent mentioned in the following table are well mixed in this order, and the mixture is mixed with a small amount of water, granulated by nieans ofagranulator and dried, whereby each granule is obtained. ln a practical use, the granule is spread as it is.

Active ingredient Binder Diluent Com- (1) 2 Sodium ligninsulfonate l Clay 97 pound do. (2) 5 do. 2 Clay 93 Example 8: Dust In a mixing ratio mentioned below, a solution of each compound in a small amount of acetone is well mixed with 200 mesh talc, and thereafter evaporation of acetone gives each dust. In a practical use, the dust is .ea sa i lis Active ingredient Diluent Compound (3) 2 Talc 98 do. (4) 4 Talc 96 The following test examples are given in order to substantiate a pesticidal effect of the present compound on insects and fungi.

Test Example 1: Lethal Effect on Carmine Mite (Tetranychus Telarius) Many of carmine mites were made parasitic on mottled kidney beans at a 2 leaves stage days after the sowing. Into each aqueous dilution of the present compounds in a form of a wettable powder, were dipped leaves of the bean, on which the mites were parasitic, for 1 minute, and were given water in order not to be died. After 48 hours, the dead and alive were observed microscopically to calculate LC (medium lethal concentration). The results are as shown in the following Table.

LC (Dilution times) Compound No.

AAAAA MANN- vvvvv Test Example 2: Insecticidal Effect on Mites in the Soil Treatment In a flower pot having about 10 cm in diameter, mottled kidney beans were grown up to a 2 leaves stage, and the present compounds in a form of 5 percent granules were spread near the root thereof in a ratio of 4 kg/lO ares. According to the lapse of days, adults of carmine mites (Tetranychustelarius) were parasitic thereon, and after 48 hours, the dead and alive of the mites on the leaves were observed microscopically. The results are as shown in the following Table.

gays elapggg and lethal ratio 1%) Comafter after after after after pound No. one day 4 days 7 days I l days 16 days (I) 26.4 96.6 88.9 94.7 100 (2) 56.7 73.4 82.1 96.4 92.3 I (3) 12.4 67.3 100 I00 87.3 (4) Y 21.3 92.4 88.3 67.4 53.4 (5) 56.3 100 I00 100 96.7

Test Example 3: Lethal Effect on Smaller Brown Planthoppers (Laodelphax Striatellus) Rice plants cm to 20 cm tall) which had elapsed 15 days after germination were dipped into each aque 5 ous dilution of the present compounds in a form of emulsifiable concentrates, for 1 minute, and after airdrying, were placed into a glass tube. Thereafter, 20 to 30 planthoppers were released therein, and covered with a wire net. After 24 hours, the dead and alive were recorded to calculate LC The results are as shown in the following Table.

Compound No. LC (Dilution times) Effect on Smaller Brown Planthoppers Test Example 4: i in the Soil Treatment Each 6 percent granules of the present compounds was spread in a ratio of 6 kg/lO ares near the root of rice plants grown at the tillering stage in an l/100,000

I Wagners pot, and adults of the planthoppers were released according to the lapse of days and covered with a wire cage. After 24 hours, the dead and alive were recorded. The results are as shown in the following Table.

after 7 days ll days 15 days Test Example 5: Effect on Green Peach Aphids (Myzus Persicae) in the Soil Treatment Many of the aphids were made parastic on chinese cabbages grown in a pot 1 month after the sowing, and each 5 percent granules of the present compounds was spread at a rate of 6 kg/IO ares near the root thereof. After 3 days, the dead and alive were recorded to calculate the lethal ratio. The results are as shown in the following Table.

Compound No. Lethal ratio (l) 100 (3) 0 Dimetoate 100 Test Example 7: Effect on Various Tortrixes and Aphids in a ratio of 7 g/tree near the root of a -year-old apple tree. The following results were obtained 5 days after the spreading.

Number of the alive parasite per 500 Number of the parasite before spreading per (3 1000 40 4.7 (4) 1000 40 5. l (5) 1000 40 9. 3 *2-( l-Methylheptyl)- 4,6-dinitrophenyl I000 40 4.2 crotonate Non-treatment 40 54.1

Note: A commercially available fungicide as Karathane.

Test Example 9: Controlling Effect on Rice Blast (Pyricularia Oryzae) On rice plants grown up to a 4 leaves stage in a 9 cm flower pot, was sprayed each emulsifiable concentrate l of the present compounds in a ratio of 10 ml/pot by i 5 means of a spray gun. After 24 hours, the spore suspension of rice blast (Pyricularia oryzae) cultured in an oatmeal medium was inoculated by spraying. The number of spots produced on a top of the leaf was counted to know the controlling effect. As is clear from the results shown in the following table, the present compounds stand comparison with a commercially availa bl ghemical i n g2 controlling effect.

500 leaves leaves after 5 days Com ound o. Tortrixes Aphids Tortrixes Aphids (l)/ 250 5730 13 I50 2) I37 4250 2 273 (3) 201 4894 21 120 Test Example 8: Controlling Effect on Powdery Mildew (Sphaerotheca F uliginea) Cucumbers (variety: Aonaga-fushinari) were grown up to a 3 to 4 leaves stage in a 9 cm flower pot.

Each wettable powder of the present compounds was diluted with water to adjust the concentration of the active ingredient to 1,000 ppm, and each 10 ml per pot of the dilution was sprayed. Spore suspension of the powdery mildew was inoculated thereinto by spraying 1 day thereafter.

The degree of diseases concerning upper 4 leaves was observed after 10 days and percentage of contraction was calculated from a spotted area. As is clear fromthe results shown in the following table, the present compounds stand comparison with a commerically available chemical in the controlling effect.

2 5 Concentration Number Number of the active of of Compound No. ingredient leaves spots per (ppm) tested leaf l) 500 15 6.5 (2) 500 15 6.9 3 0 (3 500 l 5 8 .3 (4) 500 15 6.7 (5) 500 15 [0.3 *0,0-Diisopropyl- S-benzylphosphor- S00 15 6.1 othioate Non-treatment 15 83.8

' Note: A commercially available fungicide as Kitazin P.

CHz=CHCHrNH\ 0 wherein R is methyl or ethyl, and R is an alkyl having 1 to 4 carbon atoms, and an inert carrier.

2. A method for killing injurious insects in agriculture, which comprises applying thereto an insecticidally effective amount of the phosphorothioamidate of claim 1. 

1. AN INSECTICIDAL COMPOSITION WHICH COMPRISES AS AN ACTIVE INGREDIENT AN INSECTICIDALLY EFFECTIVE AMOUNT OF A PHOSPHOROTHIOAMIDATE OF THE FORMULA,
 2. A method for killing injurious insects in agriculture, which comprises applying thereto an insecticidally effective amount of the phosphorothioamidate of claim
 1. 